RESEARCH ON NACL SALINE AEROSOLS I. NATURAL AND ARTIFICIAL SOURCES AND THEIR IMPLICATIONS
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Environmental Engineering and Management Journal June 2010, Vol.9, No. 6, 881-888
http://omicron.ch.tuiasi.ro/EEMJ/
“Gheorghe Asachi” Technical University of Iasi, Romania
______________________________________________________________________________________________
RESEARCH ON NaCl SALINE AEROSOLS
I. NATURAL AND ARTIFICIAL SOURCES AND THEIR IMPLICATIONS
Ion Sandu1*, Marin Chirazi1, Maria Canache2, Ioan Gabriel Sandu3,
Marius Tiberiu Alexianu1, Andrei Victor Sandu3,4, Viorica Vasilache1
1
„Al.I.Cuza” University of Iaşi, 11 Carol I Blvd., 700506, Iaşi, Romania
2
Bolotău School, Zemeş, County Bacău, Romania
3
„Gheorghe Asachi” Technical University of Iaşi, 71 Mangeron Blvd., 700050, Iaşi, Romania
4 Romanian Inventors Forum, 3 Sf. Petru Movilă Str., 700089, Iaşi, Romania
Abstract
This paper is the first of a series of new researches on the NaCl aerosols, which includes the bibliographical analysis and synthesis
regarding the structure, the form and the sizes of the particles of the NaCl aeroions in correlation with the production procedures.
There are also analyzed some practical applications pointed out both by some ancient Greek and Roman texts and by the present-
day literature; at the same time there is underlined the existence, even from Antiquity, of an ethnoscience which led to the current
knowledge in the halotherapy field. Concerning the artificial sources of the aerosols employed in the multiple-usage
halochambers, there have been taken into consideration the most well-known procedures which are based on the mechanical
separation or erosion, followed by the physical dispersion in the atmosphere; on the breaking of the gas bubbles in the sparging
with air or other inert gases by means of the supersaturated saline solutions; on the atomization of the saturated saline solutions in
the vacuum centrifugal air separators and the carrying-away of the superficial particles resulted from solvolyses and the
consecutive anhydrizations of the structures from the surface of the halite blocks. These procedures will be included in the
subsequent research.
Key words: aerosols, ethnoscience, halotherapy, NaCl, particle size, sources
Received: February, 2010; Revised final: May 2010; Accepted: June, 2010
1. Introduction on the environment conditions, respectively, the
atmosphere aerosols present a dimensional
The NaCl aerosols resulted from naturals distribution and a somewhat steady concentration
sources (marine aerosols and saline aerosols from salt because of the difference between the production
mines) or artificial sources (halochambers, saline speed and the loss speed, all these being considered
devices or inhalers) are polydispersed systems with as a result of the condensation, coagulation,
special nano-structural properties and with multiple peptization, electroneutralization and sedimentation
practical implications (for example, in the prophylaxis (destabilization) processes, respectively etc. (Sandu
and therapy of some respiratory affections, in the et al., 2003; Ştefan, 1998).
improvement of the parameters of the cardio- A special feature of these particles is their
respiratory apparatus as well as of the psycho- chemical composition, which varies in time and
neuromotory parameters, in the purification and the results from the interaction with the water dipoles
improvement of the quality of the atmospheric air and with other particles or ions, an interaction which
etc.). is correlated with the form and size of the aerosol
Depending on the type of the source, the (Sandu et al., 2003; 2009a; 2010a). Thus, for
activity of the particles and their life cycle as well as therapeutic environments there are used gaseous
*
Author to whom all correspondence should be addressed: e-mail: sandu_i03@yahoo.comSandu et al./Environmental Engineering and Management Journal 9 (2010), 6, 881-888
sub-micronic micro-dispersions both as ”wet- of the source), the rate of coagulation or
aerosols” and ”dry aerosols” while for ambiental sedimentation etc. (Sandu et al., 2003; Ştefan, 1998).
conditions there are employed especially the last Therefore, a specific characteristic of these
ones generate the ”fresh air effect”. nano-dispersions is the continuous structural
Depending on the characteristics of the modification due to the electrostatic and stereo-
source and on the environment conditions in which specific interactions with the dipoles and the
they are obtained, respectively, the aerosols have aircations existing in the dispersion medium.
variable forms, granulometries and concentrations. The dynamics of these processes is
One source, especially an artificial one, is determined by the intensity of the exogen factors. In
characterized by three specific zones, namely, the aqueous liquid mediums the size of the particles
active layer, the diffused layer and the residual or varies from the average diameter of the ”aquated ion”
passive layer, zones which are differentiated by the (Na+(aq) and Cl-(aq), respectively) up to some tens of
activity of the aerosols as well as by the concentration microns of a cluster-type ionic nanostructure
and sizes of the particles, respectively (Sandu et al., [(NaCl)nxH2O]-(aq), the so-called ”solion” while in the
2004a; 2004b). gaseous mediums where there are only ”solions” with
The saline aerosols resulting from natural or various diameters and structural forms, the size of the
artificial sources, used especially both for various particles ranges from tenths of microns to tens of
treatments and for prophylactic purposes as well as microns (Sandu et al., 2010). The various structure of
for increasing the performances of the human the ”solion” particles in the gaseous mediums is due
subjects, must have a certain activity, i.e., a certain to the different degree of hydration with water dipoles
level of concentration and a certain well-controlled and to their way of suprastructuring, taking multiple
domain of granulometry, respectively. forms with spatial structures similar to snow flakes
Concerning the usage of the aerosols there is only at a nanostructural level. The multiple structural
an interesting history that proves the existence of an arrangement (Sandu et al., 2002) is considered to be
ethnoscience, which has generated during some time the result of the compatibility between the cubic
periods various applications of the halite, salt marsh crystalline lattices of the sodium chloride and of the
and saline aerosols. Moreover, this ethnoscience has pentahydrol water (H2O)5.
led to a new branch, i.e. the halotherapy, very much Depending on their activity and life period,
used now-a-days, and having great development respectively, the aerosol particles have a somewhat
prospects in the future. steady dimensional distribution which is the result
This paper presents a series of aspects between the production speed and the loss by
connected with the structure of the aerosols, with the different processes. From this view point, they can be
obtaining methods and with the practical implications divided in five groups or dimensional levels which
known from Antiquity till the present times, data correspond to some various measuring methods and
which are very important for the development of techniques; here they are.
some researches regarding the halotherapy, researches small simple ions with diameters under 0.5 nm
which will be discussed in some future papers. which can be determined only in solution or
smelt by electrochemical methods (Gulea,
2. The size and form of the NaCl aerosols particles 1994);
Aitken particles with diameters between 0.5 and
From a chemical view point of view, the 50 nm, detected with the Aitken Particle
sodium chloride is a strong saline electrolyte with a Counter (Junge 1963) or by means of the mass
high wettability and a limited solubility in water (35.7 spectroscopy (Mitchell and Nagel, 2004);
g/100 g H2O at 0C and, respectively, 39.12 g/100 g average-size particles, with diameters between
H2O at 100C) or in other polar solvents; sodium 50 and 100 nm, detected with the Laser (phase)
chloride can exist, both in the liquid and gaseous Doppler System (Mitchell and Nagel, 2004),
environments, as crystalline nano-dispersions Angular Intensity Light Scattering (Mulholland
interacting with the dipoles of the dispersion medium et al., 1985) and Quasi-elastic Light Scattering
which gives them a variable chemical structure, under (Mitchell and Nagel, 2004) methods;
a glomerural form, with a specifically negative charge large particles, with diameters between 100 and
(Sandu et al., 2004; 2009a; 2010a). 1,000 nm, detected with the Laser
Since the particles have a negative charge, Diffractometer (LD) (Mitchell and Nagel, 2004),
their life cycle varies from a few minutes to a few Electronic Microscopy Transmission (MET)
days, depending not only on a series of external or (Lettieri and Hembre, 1989) and Electrical
environmental exogen factors, i.e. humidity, Sensing Zone (ESZ) (Mitchell and Nagel, 2004)
temperature, pressure, light, presence of some methods;
dispersions with positive charge as well as of the huge particles, with diameters more than 1,000
organic ones, but also on some endogenous factors, i. nm (up to some tens of microns), detected with
e. the form, the side and the nature of the grains the Electrical Mobility Analyser (Kinney et al.,
(powders), the method of obtaining or the type of the 1991) and Optical Microscopy/image Analyser
source, the production speed (capacity or the output (Hartman et al., 1991; Hartman and Doiron,
882Research on NaCl saline aerosols
1992; Lettieri et al., 1991; Thom et al., 1985) In an organism salt performs a series of
methods; actions in accordance with the concentration level in
The classification of the NaCl aerosols the biotic system, with its mineral composition, with
according to the dimensional groups and to the form its retention and elimination capacity and with the
is shown in Table 1. coagulating capacity of the gelling systems. High
It is known a method and a device used for concentrations of salt also have antibacterial,
determining the concentration of NaCl aerosol in antimicrobial, and even antimycotic activities. This is
various natural and artificial halochambers (Pascu et how we explain, besides the therapeutic action, its
al., 2009b). These were used in the study of different various uses in food preservation (Chervinskaya,
wet and dry aerosol sources (Sandu et al., 2003; 2007; Hedman et al., 2006; Sandu et al., 2002; 2003;
2004b), but also in the study of the influence of 2006; 2009a; 2010a). More details concerning these
exogenous factors (Sandu et al., 2003; 2004a). actions are given below:
action on the nervous system through the ionic
3. From ancient application to modern effects upon axons and neuronal cell bodies,
halotherapy reducing the pain (dental diseases, neuralgias, etc.);
action upon mucosal surfaces, in particular their
A series of comparative studies (Sandu et al., microbiotic systems, with effects extending to
2009a; 2010a), presenting the data obtained from internal areas (such as salivary glands, middle and
ancient writings and from ethnographic surveys, have inner ear, sinus cavity, gingival zone, oral cavity,
concluded that salt is being used with multiple etc.) and physical lesions (including stings, bites,
applications (as natural brine or solid salt). Among cuts, etc.).
these we mention: food conservation, treatment of antimicrobial actions in cases of tonsillitis, sinusitis
different diseases, treatment of wood and animal and otitis, as well as infections after bites, stings,
skins and water purifying, applications which are etc. The mechanisms include the astringent effect
used as traditional procedures in the countryside until (i.e., protein denaturation), inhibition of the
today. microbial metabolism as well as the increased
The other important objective of this study is efficiency of the leukocyte system;
to highlight the validity of the corresponding ancient antagonism of rheumatic processes, by its effects on
and current practices, analyzed from the scientific the erythrocyte sedimentation rate (ESR) and by the
perspective of biochemistry and biophysics. The modulation of the processes in the circulatory
continuation of the ancient halotherapeutic practices system; effects on certain antigens, as well as the
in rural Moldavia proves that the area under stimulation of specific antibodies, by increasing
discussion still has a true ethnoscience in the field. their affinity for bacterial and viral proteins toxic
Simple people in the Moldavian villages know the bacterial components;
beneficial effects of salt in the treatments against effects on the coagulation process, which account
certain diseases, without being interested in providing for the hemostatic action.
scientific explanations for those effects. All these applications are considered to be
The use of the halite and brine in various based on the saline effect of NaCl as a strong
therapies, as such or as powders and solutions (natural electrolyte that can affect, at certain levels of
or artificial salt water) in ancient times and in the concentration, the epithelial system and the microbial
current traditional areas or in modern preparations flora as well as the humoral system and the superficial
(pomades, tooth pastes, soap, sticks, etc.) has a nerves (Sandu et al., 2009a; 2010a). The NaCl
scientific explanation in the properties of the nanostructures may take three forms: as dry
nanostructures. These nanostructures may be glomerulate microparticles (dry aerosols); as hydrated
dissolved or dispersed in the usage systems whose microparticles (hydrated solvions or aerosols with a
negative charge is usually represented by what we monomolecular layer of water); as nanostructures
may call ”solvions.” The latter become effective in dispersed in aqueous systems, going as far as simple
the osmotic processes that influence the mechanisms hydrated ions (Na+(aq) and Cl-(aq)).
of the dysfunction recovery. These actions begin at The glomerulate (grouped in small, dense
the epithelial surfaces but can also involve more clusters) structure, which depends on the degree of
specific metabolic processes. hydration, can take shapes that resemble snowflakes.
Table 1. The dimensional groups and the forms of the NaCl aerosols
Type of Particle Ions Aitken Average-size Large Huge
Large ions and
Condensate Coagulated Sedimentable
Form Small simple ions small ionic
particles particles particles
aggregates
Radius of particle
< 0.5 0.5...50 50...100 100...1000 > 1000
(nm)
883Sandu et al./Environmental Engineering and Management Journal 9 (2010), 6, 881-888
The shape and size of such nanoparticles is the specific nanostructuring of the crystallites with
determined by a series of environmental factors, superficial negative charge, capable of osmotic
mainly by the ones depending on the acid-basic processes through the membranous systems of the
reactivity of the environment. The nanodispersions of internal organs. Also, the membranous systems based
the solvions in the biological extra-cellular fluids can on polypeptide structures with reactive support have
reach a concentration of cca. 0,9% NaCl, whereas in an influence on the re-formation of the NaCl
the intra-cellular fluids the concentration is lower due structures of a solvion type, due to the fact that such
to the specialized membrane channels that allow the systems contain amphionic groups. As a result of the
direct and/or the reverse osmosis of the Na+(aq) cations electrostatic interactions, the polypeptides enhance,
which, comparatively, have ionic volumes larger than by their isoelectric point, the ordering of flexible and
those of the Cl-(aq) anions. mobile structures. Thus, functional biotic
The nanoparticles dispersible in the air microstructures of certain tissues are optimized
behave as ”negative aeroions”, as they are (Sandu et al. 2009g; 2010). Several concrete
glomerulate nanocrystalites, either dry or hydrated, applications are known in cases such as the lumbago,
with negative surface charges. Such negative solvions the stomach, the liver and the pancreas aches. These
have beneficent effects on organisms. Moreover, in applications are added, in combination with vinegar
the air they interact with organic nanodispersions, and wine, to the sodium chloride and to the small
either dry or with one-layer hydration, which behave amounts of bronze or copper filings, and are
as ”positive aeroions”, such as the ones resulting from consumed after decanting. Nevertheless, we do not
pyrolysis, cracking, or burning of cigarettes, in which have enough explanations for such treatments
cases the toxic effect of smoke is eliminated by the (Poryadin et al., 2002). What we may observe here is
electrostatic destabilization of the dispersion (Alfoldy that the copper filings can be anodically dissolved
et al., 2002; Sandu et al., 2009a; 2010a). (Cu0 Cu2+ + 2e-) in the presence of the NaCl
Ethnographic surveys mention the fact that electrolyte, in a solvion form (Cu2+(aq)) that interacts
most of the cataplasms used in treatments, such as with the wine tannins in an acid medium, the result
pouches with salt and even thin strata of salt, should being molecular species that are hard to hydrolyze or
be warmed to an optimal temperature for the human dissolve. Copper filings provide completion of the
body (around 50-60 degrees Celsius). Usually, the macroelement deficit in certain enzymatic processes.
users do not think about the thermal effect. It is true Also, in the presence of the NaCl as a highly effective
that the thermal shock produces certain electrolyte, copper filings prove to play an important
improvements, but only during the application. part in the elimination of toxicity from the red tannin-
Therefore, the curative effect is mostly due to the rich mountain wines (Sandu et al., 2009a).
aeroions emanated by the salt and inhaled into the More recently, NaCl with KCl and other
lungs and thus acting upon the epithelia through salts are used in artificial halochambers, for terapy
osmosis. It also activates the immune systems, and in order to improve the performance of
including the leukocytes; it stimulates the formation sportsmen. Thus, the KCl aeroions are fundamentally
of antibodies and it improves the potentially involved in a massive amount of body processes, such
pathogenic biochemical processes. In this sense, the as fluid balance, protein synthesis, nerve conduction,
nanostructural NaCl aeroions play the multiple role of energy production, muscle contraction (conversion of
an antigen at the level of certain organs, producing glucose into glycogen), synthesis of nucleic acids and
most of the previously mentioned effects control of heartbeat, reducing the blood pressure. In
(Chervinskaya, 2007; Hedman et al., 2006; Poryadin many of its roles, potassium is opposed by sodium,
et al., 2002; Sandu et al., 2002; 2003; 2006; 2009a; and the two positive ions are jointly balanced by the
2010a). negative ion, chloride (He et al., 2005; Matsui et al.,
Another therapeutic application that needs to 2006; Pikilidou et al., 2007).
be explained is the use of the fine dispersions of salt
having as basis vinegar, wine and oil. We know that 4. Present-day procedures for producing the saline
the solubility and the formation of certain crystalline aerosols
solvates and of certain hydrolyzable molecular
species formed in situ in a dispersed system depend Besides the halochambers from the salt
on the pH. They also depend on the presence of ions mines, very much used both for prophylactic purposes
other than sodium and chloride, on temperature and and in the therapy of some diseases, there have been
on other factors that favor the formation of certain drafted after 1990 a series of procedures for obtaining
nanostructural solvated aggregates of NaCl. In the the saline aerosols on the basis of NaCl as such or in
latter the superficial single layer of water has a mixture with some inorganic or organic compounds,
dipolar profile with external negative charge, which with pre-established chemical compositions
favors a behavior similar to the one of the dry depending on the application type. Depending on the
negative aeroions that stimulate the recovery from production physico-mechanical, hydric and thermal
certain diseases by biochemical mechanisms specific processes, these procedures are classified into four
to the inorganic antigens. Vegetable oil as well as groups; here they are:
wine and vinegar create a mildly acidic pH and favor
884Research on NaCl saline aerosols
mechanical separation or erosion, followed by frames, honeycomb-type structures or diaphragms,
physical dispersion in the atmosphere from the platforms, cross walls),
halochamber with the help of a gas flow, of the - the humidity and the temperature of the carrying
saline systems under the form of esorated gaseous agent, the temperature and the humidity
precipitates, fine micro-crystallites, extruded at which the dispersed saline material is being
micro-pellets or pellets obtained through kept,
recrystallization from supersaturated solutions by - the operating conditions of the installation (the
means of the hydro-thermal processes or by the ratio between the operating period and the non-
evaporation of the solvent from the thin layers of operating one) etc.
concentrated solutions accomplished by dripping In the case of the large crystals, the
(Clark et al., 1996; Hickey, 1994; Pascu, 2002a; processes of deliquescence and efflorescence which
2002b; 2003a; 2003b; 2003c; 2006; 2007; 2008; take place during the non-operating periods improve
2009a); the discharge or the capacity of the installation.
breaking of the gas bubbles in the barbotage With this end in view one knows the SALIN
processes with air or other inert gases by means of devices manufactured by the TehnoBionic Company,
the supersaturated saline solutions (Joutsensaari et Buzău (Pascu, 2003a, 2007; 2008; 2009a), devices
al., 2001); which, by means of ventilation, carry out the particles
atomization of the saturated saline solutions in resulted from solvolyses and the consecutive
vacuum centrifugal air separators, followed by the anhydrizations from the surface of the pellets
physical dispersion with the help of an air flow obtained by recrystallization from the supersaturated
(Katusik et al., 2000; Merchat, 1994); solutions of NaCl as such or in the mixture with
carrying-away of the superficial particles resulted others salts (KCl, MgCl2, CaCl2, KI, etc.).
from solvolyses and the consecutive In what the second group of methods is
anhydrizations of the surface structures as a result concerned, there are four stages (Fig. 1) for producing
of the air carrying through the holes and grooves the NaCl aerosol particles (Moore et al., 1954;
done in the bars or parallelipipedic blocks of Pruppacher and Klett, 1978). The chemical
halite, arranged as screens on the walls of the composition of the aerosol particles depends on the
halochamber (Albiach, 1995; Belkin, 2005; components existing in the supersaturated saline
Konovalov, 1993; Sandu et al., 2009b; 2009c; solutions while the micro-physical and nano-
2009d; 20092; 2010b; 2010c). structural characteristics depend on the temperature of
In the case of the first group of methods, the the saline solution and of the bubble-generating agent,
discharge, the capacity and the output of the source on the pressure of the gas as well as on the size of the
(installation, device or apparatus) depend on a series gas bubbles. For instance, one knows that the number
of factors such as: of the aerosol particles produced by the breaking of
the gas bubbles increases with the increase of their
- the degree of separation of the micro-crystallites, sizes. A bubble with a size of some millimetres forms,
- the intensity of the gas flow, by breaking, some hundreds of particles, and the
- the complexity of the installation and the average frequency of their forming is 25 - 100
geometric section of the active zone (filters, particlescm-2s-1 for a slight gas sparging (Blanchard,
1969).
Fig. 1. Stages for the production of the saline aerosol particles in the barbotage system by means of the mechanism of the gas
bubbles explosion: a. Formation of the thin layer at the surface of the saline solution (gas bubble dipped at the surface); b. Bubble
breaking with the formation of a solution fragment; c. The unstable jet produces the breaking and the formation of some other
fragments from the adjacent layers; d. Formation of the fine particles after the evaporation of the solvent from the fragments of the
solution dispersed in the siccativant gaseous medium
885Sandu et al./Environmental Engineering and Management Journal 9 (2010), 6, 881-888
With the third group of methods, depending carrying-away of the superficial particles from the salt
on the diameter of the spray nozzle, correlated with blocks.
the discharge of the jet as well as with the value of the In what the characteristics of the aerosol
vacuum pressure and temperature, one can obtain particles are concerned, these are determined not only
particles with dimensional distributions preferential by the source but also by the environmental factors.
for one of the four dimensional groups. By Accordingly, there are discussed the functional
comparison with the first two groups of methods, the characteristics, specific to a source of saline aerosol
last one has the disadvantage both of using some (the size and density of the aerosol, the forming rate
complex equipment and of high production price. of the particles, the source output, the factor for the
The fourth procedure group which implies enrichment of the gaseous medium, the life cycle of
the carrying-away of the superficial particles resulted the particles). All these are used to choose the
from the consecutive processes of solvolyses and optimal generator model and the nano-structural and
anhydrization of the superficial structures from the micro-physical properties of the aerosols (the aerosol
holes and grooves done in the parallelepipedic blocks concentration and its variation in time, the
of halite, arranged as screens on the walls of the dimensional distribution of the particles, the dynamic
halochamber, taking over to a certain extent the behaviour of the aerosol, the diffusion, mobility and
structure and the functionality of the neutral system of the drift speed of the particles as well as the limit
the halochambers from the old salt mines. With this humidity of the environment at which the formation
end in view there exist a series of artificial salt mines of the condensation nuclei starts). These lead to a
in which the particles from the surface of the salt proper understanding of their implication in the
blocks are taken over by conveying the air by means climatic environments.
either of the conventional jets or of an air jet from a There are presented the three specific areas
blower (Albiach, 1995; Anderson, 1995; Belkin, of a climatic environment activated by a source,
2005; Clark et al.,1996; Gafurov, 1990; Hickey, 1994; namely, the active layer (the area near the source),
Kabanov, 1992; Klaus, 1993; Konovalov, 1993; characterized by high concentration where all four
Sandu, 2009a; 2009b; 2009c; 2009d; 2009e; 2009f; dimensional groups of particles coexist; the diffused
Wills, 1995). layer, an extended one, characterized by a dynamic
state of the distribution of the dimensional domain
5. Conclusions and of the life cycle, having all parameters in a
continuous variation; the residual or passive layer
This paper represents the first report from a (the most remote from the source or existing in some
series which includes the state-of-the-art analysis and hardly accessible zones) with a small and usual
synthesis concerning the structure, the form and the uniform concentration, characterized by a stationary
sizes of the particles of NaCl aeroions in correlation state of the distribution of the dimensional domain
with the production methods and their practical and of the life cycle.
applications. The dominant processes in these three zones
Depending on their activity and life cycle, are: the condensation based on chemical reactions and
respectively, the aerosol particles have a somewhat which form particles from the nucleation group, the
steady dimensional distribution, which is the result condensation or the peptization of the primary
between the production rate and the loss during particles, thus resulting the accumulation group, and,
different processes (condensation, coagulation, finally, the coagulation and monolitization of the
electro-neutralization, sedimentation/destabilization large and huge particles, thus resulting the group of
etc.). From this point of view, these particles are the sedimentable particles. Among these, the greatest
classified in five groups (simple ions, Aitken particles, importance in the establishment of the climatic
small particles, average-size particles, large and huge environments with a therapeutical and ambiental
particles). purpose is awarded to the group of the accumulation
According to the historical sources and the particles that, in fact, form the diffused layer as well
present-day literature, the salt has multiple as by the group of the very small particles from the
applications either as brine or marsh, under a solid active layer.
form or as aerosols, being used for the treatment of
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